CN102443701B - Clean metallurgic comprehensive utilization method of iron vitriol slags - Google Patents

Clean metallurgic comprehensive utilization method of iron vitriol slags Download PDF

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CN102443701B
CN102443701B CN201010503846.9A CN201010503846A CN102443701B CN 102443701 B CN102443701 B CN 102443701B CN 201010503846 A CN201010503846 A CN 201010503846A CN 102443701 B CN102443701 B CN 102443701B
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China
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zinc
iron
ammonium chloride
iron vitriol
slag
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CN201010503846.9A
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Chinese (zh)
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CN102443701A (en
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张懿
巨少华
张亦飞
薛佩毅
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中国科学院过程工程研究所
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    • Y02P10/22
    • Y02P10/232
    • Y02P10/234
    • Y02P10/236

Abstract

The invention relates to a clean metallurgic method for treating iron vitriol slags produced during the processes of smelting zinc and removing iron by a wet method and recovering the valuable metals. The method comprises the following steps: 1) intermediate temperature roasting the waste slags to decompose iron vitriol and zinc ferrite in the slags; 2) selectively leaching the roasted iron vitriol dregs by ammonium chloride and an ammonia aqueous solution to obtain the leachate containing zinc, copper, lead, cadmium, silver and the like as well as leached slag containing iron and arsenic; 3) reducing and recovering the copper, lead, cadmium and silver in the leachate by zinc powder to obtain a zinc ion-rich ammonium chloride solution; 4) extracting zinc in the ammonium chloride solution by P204, back extracting by sulfuric acid to the solution, carrying out electrodeposition to obtain cathode zinc with high purity; 5) leaching the leached slags in the step (2) by a sodium hydroxide solution to obtain the alkali leached slag with full detoxification which can be taken as high quality low ferrosilicon ore concentrate or an ironmaking raw material. The method can effectively recover the valuable metals in the iron vitriol slags, the treatment process is clean, and the comprehensive utilization method can effectively solve the stock and pollution problems of iron vitriol dregs.

Description

The clean metallurgical method of comprehensive utilization of iron vitriol slag

Technical field

The invention belongs to metallurgical dangerous solid slag process field, particularly a kind of clean metallurgical method fully utilizes the method for iron vitriol slag, also can be used for processing the iron vitriol slag containing heavy metal of other type.

Background technology

China is current faces outstanding heavy metal pollution problem, and coloured lead-zinc smelting is the key industry of Heavy Metal Pollution.China's zink sulphide resource associated element is more, ore type complexity, and often association has the poisonous and harmful impurity such as cadmium, lead, arsenic and mercury, thereby has increased the difficulty reclaiming in smelting process.At present, zinc metallurgy method in the world is mainly divided into pyrogenic process and the large class of wet method two, and 80% ultimate production is produced by wet processing in the world.Conventional wet smelting process comprises roasting, leaching, solution purification, electrolytic deposition, five operations of cathode zinc founding.The waste residue of output mainly contains iron vitriol slag, plumbous silver-colored slag, cadmium slag etc., and because common associated element comprehensive reutilization level is not high, a large amount of common association heavy metal elements have entered in waste, have brought day by day serious environmental problem.The data of announcing according to coloured TIA of China, China in 2009 produces zinc ingot metal and reaches 4,416kt, and wherein electric zinc output accounts for 65%, and in China's Zinc Hydrometallurgy Process, average every production 1t electricity zinc on average will discharge the iron vitriol slag of 0.3t left and right.The iron vitriol slag total amount of calculating thus the annual discharge of China reaches 1 × 10 6t left and right, accumulative total reaches 5 × 10 6more than t, the overwhelming majority is not utilized effectively, and saves as master to pile [1-3].Therefore, this dangerous solid waste of comprehensive utilization iron vitriol slag has become the important directions of home and abroad environment Comprehensive Treatment of Pollution.

At present, the major programme of industrialized processing iron vitriol slag is exactly fuming volatilization method in the world, comprises rotary kiln evaporation technique, Ausmelt technique, fuming furnace volatilization technique and low shaft blast furnace technique [4-9]; These thermal process all exist energy consumption compared with problem high, that fixed investment large, metal recovery rate is lower, the problem of environmental pollution that the volatilization of Cd and As also can cause etc.

Up to the present, the patent aspect processing iron vitriol slag is more both at home and abroad, but these patents are having certain deficiency aspect metal recovery rate, cost recovery or environment friendly.As patent EP 1098999-A1 proposes after roasting, water leaches, then reclaims valuable metal through the method for neutralization precipitation, sulfide precipitation, ion-exchange or extraction, and technique is simple, but shortcoming is that the silver-colored and plumbous rate of recovery is low; Patent US2004118248-A1 proposes first iron vitriol slag to be adopted to alkaline purification, then with acid neutralization, the method that makes valuable metal stripping and reclaim, technique can be adapted to the processing of the different multi-metal complex waste residue of handling properties, but in acidleach process, unavoidably there is the stripping of iron, and can produce the iron waste residue containing heavy metal when deironing again; Patent CN1221800 proposes iron vitriol slag roasting, through leaching, and Centrifugical extraction separating indium iron, to reclaim the method for indium, its shortcoming is the stripping of a large amount of iron, makes follow-up deironing produce the recovery of a large amount of scums and heavy metal ion very difficult; Patent WO8803911-A has proposed to use CaCl under high temperature peracid high pressure 2the method that leaches valuable metal in iron vitriol slag, has obtained good metal recovery rate, and has suppressed the stripping of iron, but shortcoming is to adopt high temperature peracid high pressure to leach, and cost is higher.For the iron resources in comprehensive reutilization iron vitriol slag, by iron vitriol slag, ironic hydroxide and the gac etc. after roasting, water logging, neutralization precipitation is mixed and made into hydrogen sulfide adsorbent in patent KR8902856-B proposition, its key issue is that the purity of ironic hydroxide product is not high, and in iron vitriol slag, other resources do not obtain efficient recovery; Patent CN101407355A proposes acidleach iron vitriol slag and reclaims valuable metal, leached mud is mixed with sulfuric acid under microwave radiation, add again water and iron compound, oxidation makes iron be converted into trivalent, bodied ferric sulfate is made in hydrolysis, and the key issue of this technique is also that the rate of recovery of product purity and other heavy metal is not high.

Therefore, from end, the iron vitriol slag of zinc hydrometallurgy gained is administered the important directions that remains China environmental protection, pollution emission reduction, resource high-efficiency comprehensive utilization and recycling economy.

The present invention proposes iron vitriol slag waste residue to carry out medium temperature roast, and siderotil and zinc ferrite in slag are decomposed; Adopt again ammonium chloride and ammonia soln to leach, obtain containing the leach liquor of zinc, copper, lead, cadmium and silver etc. and the leached mud of iron content and arsenic; Reclaim copper, lead, cadmium and the silver in leach liquor with zinc powder reduction, obtain being rich in the ammonium chloride solution of zine ion simultaneously; With the zinc in P204 extraction ammonium chloride solution, then use sulfuric acid back extraction to solution, obtain high-purity cathode zinc through electrodeposition; With sodium hydroxide solution leaching ammonium chloride leached mud, the alkali being detoxified completely soaks slag and can be used as high-quality iron ore concentrate or iron-smelting raw material use.Can effectively reclaim valuable metal in iron vitriol slag and iron resources wherein, thus the pollution problem of storing up that thoroughly solves waste residue etc.

Summary of the invention:

The object of the invention is to provide a kind of method that fully utilizes iron vitriol slag.

The iron vitriol slag method producing in comprehensive utilization zinc hydrometallurgy iron removal of the present invention, concrete steps are:

1 pair of waste residue carries out roasting 0.5-3 hour at 400-800 DEG C, makes siderotil and zinc ferrite in slag be converted into soluble zinc sulfate, lead sulfate and undissolved ferric oxide in ammonium chloride.Reaction formula is:

K 2Fe 6(SO 4) 4(OH) 12→3Fe 2O 3+K 2SO 4+3SO 3↑+6H 2O↑

ZnO·Fe 2O 3+SO 3→3ZnSO 4+Fe 2O 3

The gas discharging can be eliminated by water or alkali liquor absorption the pollution of waste gas.

The ammonium chloride that 2 use volumetric molar concentrations are 3-7M and the ammonia soln of the 0.1-1M iron vitriol slag after to roasting leaches 0.5-3h at 95-120 DEG C, obtains containing the leach liquor of zinc, copper, lead, cadmium and silver etc. and the leached mud of iron content and arsenic.Reaction formula is:

ZnO+4NH 4 +→Zn(NH 3) 4 2++H 2O+2H +

Pb 2SO 4+4Cl -→PbCl 4 2-+SO 4 2-

Ag 2O+2H ++8Cl -→2AgCl 4 3-+H 2O

CdO+NH 4 +→Cd(NH 3) 2 2++H 2O

CuO+2NH 4 +→Cu(NH 3) 4 2++H 2O

In 3 use ammonium chloride leach liquors, copper, lead, cadmium and silver-colored total mole number 1.0-3.0 zinc powder doubly reduces 10-60 minute to reclaim copper, lead, cadmium and the silver in leach liquor at 30-80 DEG C, obtains being rich in the ammonium chloride solution of zine ion simultaneously:

Me n++Zn→Me+Zn 2+

Wherein, Me n+represent Ag +, Cu 2+, pb 2+or Cd 2+.

4 adopt two-(2-ethylhexyl) phosphoric acid (P2O4) and the isodecyl alcohol of 5-10% volume ratio or the kerosin of tributyl phosphate (TBP) containing 20-30% volume ratio, 40-50 DEG C, compare under the condition of O/A=0.5-2, extract the zinc in above-mentioned ammonium chloride leach liquor through two-stage, use again the back extraction of 100-200g/L sulfuric acid to solution, obtain through electrodeposition the cathode zinc that purity is higher.The type reaction wherein occurring is as follows:

Extraction process Zn (NH 3) 4 2++ 2HA (o)→ ZnA 2 (o)+ 2H ++ 4NH 3

Back extraction process ZnA 2 (o)+ H 2sO 4→ Zn 2++ 2HA (o)

Electrolytic deposition process 2Zn 2++ 2H 2o → 2Zn+O 2+ 4H +

The sodium hydroxide solution of 5 use mass concentration 10-30% leaches the leached mud of gained in 0.5-2 hour step 2 at 100-160 DEG C, and the alkali being detoxified completely soaks slag and can be used as high-quality iron ore concentrate or iron-smelting raw material use.Reaction formula is:

SiO 2+NaOH→Na 2SiO 3(aq)

As 2O 3+NaOH→2NaAsO 2(aq)+H 2O

The present invention is different from existing iron vitriol slag treatment process, in order effectively to fully utilize iron vitriol slag, reduces energy consumption and supplies consumption simultaneously, obtains good environmental benefit and economic benefit, and the present invention proposes roasting-NH 4cl leaching-zinc powder reduction is reclaimed plumbous silver-bearing copper cadmium-extraction electrodeposition and is reclaimed the novel process that zinc-alkali soaks desiliconization arsenic.Be expected to thoroughly solve the severe contamination problem that iron vitriol slag is stored up in a large number.

Brief description of the drawings

Fig. 1 is the schematic flow sheet of the method for comprehensive utilization iron vitriol slag of the present invention.

Embodiment

For the content of patent of the present invention is better described, provide following embodiment.Iron vitriol slag in the present embodiment is the Jarosite Residues from wet zinc-making system, and its chemical composition is as shown in table 1:

The chemical composition of iron vitriol slag before table 1. roasting

Embodiment 1

By Jarosite Residues roasting 1h at 650 DEG C, it burns rear composition as shown in the first row in table 2.

The chemical composition of each operation gained slag in table 2. embodiment 1

The NH that is 6M by volumetric molar concentration 4the NH of Cl and 1M 4oH solution leaches the Jarosite Residues after roasting by liquid-solid ratio (mL/g) the condition selectivity of 10: 1, the composition of gained leached mud is as shown in table 2 the second row, the composition of leach liquor is as shown in table 2 the third line, and wherein zinc leaching rate reaches 97.5%, copper leaching rate 95.4%, silver and cadmium leaching yield 100%, plumbous leaching yield reach 93.3%; Fe and As leach hardly;

The zinc powder of 1.3 times of copper in leach liquor and ammonium chloride leach liquor, lead, cadmium and silver-colored total mole numbers is stirred 40 minutes at 50 DEG C, after reduction, the composition of liquid is as shown in table 2 fourth line, and wherein copper and the plumbous rate of recovery can reach 92%, the rate of recovery of silver raising recovery rate 80%, cadmium is more than 77%; Here the rate of recovery of silver and cadmium is low is mainly because their concentration in leach liquor is too low, and in fact, leach liquor is after repeatedly circulate silver and cadmium concentration improve, and the zinc powder reduction rate of recovery just can reach more than 90% (as described in Example 3).

Adopt the kerosin containing the P204 of 20% volume ratio and the isodecyl alcohol of 8% volume ratio, 50 DEG C, compare under the condition of O/A=3/4, extract the zinc in above-mentioned ammonium chloride leach liquor through two-stage, percentage extraction can reach 86%, raffinate composition is as shown in table 2 fifth line, use again the back extraction of 150g/L sulfuric acid to solution, obtain through electrodeposition the cathode zinc that purity is higher;

At 160 DEG C, process NH with the NaOH of mass concentration 30% 4cl leached mud, gained leached mud composition is as shown in table 2 the 6th row, and the leaching yield that calculates thus silicon reaches 75%, and the leaching yield of arsenic reaches 77%; In the scum of gained, iron content has reached 53.84%, and wherein the content of silicon-dioxide is only 5.46%, and in waste residue, the content of poisonous element is all lower than 0.1%.

Embodiment 2

By Jarosite Residues roasting 2h at 600 DEG C, it burns rear composition as shown in the first row in table 3.

The chemical composition of each operation gained slag in table 3. embodiment 2

The NH that is 5M by volumetric molar concentration 4the NH of Cl and 0.6M 4oH solution leaches the Jarosite Residues after roasting by the liquid-solid ratio condition selectivity of 10: 1, the composition of gained leached mud is as shown in table 3 the second row, the composition of leach liquor is as shown in table 3 the third line, wherein zinc leaching rate is 96.0%, copper leaching rate is 83.7%, silver leaching rate 80.5%, cadmium leaching yield are 100%, plumbous leaching yield reaches 90.2%, Fe and As leaches hardly;

The zinc powder of 1.5 times of copper in leach liquor and ammonium chloride leach liquor, lead, cadmium and silver-colored total mole numbers is stirred 60 minutes at 40 DEG C, after reduction, the composition of liquid is as shown in table 2 fourth line, wherein copper and the plumbous rate of recovery can reach 91%, the rate of recovery 75% of silver raising recovery rate 71%, cadmium;

Adopt the kerosin containing the P204 of 30% volume ratio and the isodecyl alcohol of 6% volume ratio, 40 DEG C, compare under the condition of O/A=1/1, extract the zinc in above-mentioned ammonium chloride leach liquor through two-stage, percentage extraction can reach 82%, raffinate composition is as shown in table 2 fifth line, use again the back extraction of 100g/L sulfuric acid to solution, obtain through electrodeposition the cathode zinc that purity is higher;

At 140 DEG C, process NH with the NaOH of mass concentration 20% 4cl leached mud, gained leached mud composition is as shown in table 3 the 6th row, and the leaching yield that calculates thus silicon reaches 63%, and the leaching yield of arsenic reaches 70%; In the scum of gained, iron content has reached 47.34%, and wherein the content of silicon-dioxide is only 7.50%, and in waste residue, the content of poisonous element is all lower than 0.19%.

Embodiment 3

It is 2.0 times of zinc powder reduction experiments of required reduction elements mol ratio that solution shown in his-and-hers watches 4 first rows has carried out add-on, its temperature of reaction is 50 DEG C, and the time is 1h, after reduction finishes, solution composition is as shown in table 4 secondary series, and the reduction process rate of recovery is as shown in table 4 the 3rd row.

The chemical composition rate of recovery in table 4. embodiment 3 before and after reduction

Claims (6)

1. a comprehensive utilization is from the method for the iron vitriol slag of wet zinc-making system, it is characterized in that comprising the following steps: (1), to waste residue roasting 0.5-2 hour at 400-800 DEG C, makes siderotil and zinc ferrite in slag be converted into soluble zinc sulfate, lead sulfate and undissolved ferric oxide in ammonium chloride; (2) with the ammonium chloride of 3-7M and 0.1-1M ammonia soln, the iron vitriol slag after to roasting leaches 0.5-3h at 95-120 DEG C, obtains containing zinc, copper, lead, cadmium and the leach liquor of silver and the leached mud of iron content and arsenic; (3) at 30-80 DEG C, reduce 10-60 minute to reclaim copper, lead, cadmium and the silver in leach liquor with the zinc powder doubly of copper, lead, cadmium and silver-colored total mole number 1.0-3.0 in ammonium chloride leach liquor, obtain being rich in the ammonium chloride solution of zine ion simultaneously; (4) adopt two-(2-ethylhexyl) phosphoric acid and the isodecyl alcohol of 5-10% volume ratio or the kerosin of tributyl phosphate containing 20-30% volume ratio, 40-60 DEG C, compare under the condition of O/A=0.5-2, zinc in the above-mentioned ammonium chloride solution that is rich in zine ion of two-stage extraction, raffinate is mainly ammonium chloride solution, recycles as leach liquor; Zinc in organic phase uses the back extraction of 100-200g/L sulfuric acid again to solution, obtains through electrodeposition the cathode zinc that purity is higher; (5) at 100-160 DEG C, leach the leached mud of gained in 0.5-2 hour step (2) with 10-30% sodium hydroxide solution, the alkali being detoxified completely soaks slag and uses as high-quality low-silicon iron concentrate or iron-smelting raw material.
2. comprehensive utilization according to claim 1 is from the method for the iron vitriol slag of wet zinc-making system, and wherein in step (1), optimized condition is: maturing temperature is 650 DEG C, and roasting time is 1 hour.
3. comprehensive utilization according to claim 1 is from the method for the iron vitriol slag of wet zinc-making system, it is characterized in that in step (2), optimized leaching condition is: ammonium chloride concentration is 6M, ammonia concn is 0.3M, and extraction temperature is 105 DEG C, and extraction time is 2 hours.
4. comprehensive utilization according to claim 1 is from the method for the iron vitriol slag of wet zinc-making system, in its step (3), optimized reductive condition is: zinc powder consumption is copper, lead, cadmium and silver-colored total mole number 1.5 times in ammonium chloride leach liquor, temperature is 50 DEG C, and the recovery time is 30 minutes.
5. comprehensive utilization according to claim 1 is from the method for the iron vitriol slag of wet zinc-making system, in its step (4), optimized extraction conditions is the kerosin adopting containing two-(2-ethylhexyl) phosphoric acid of 20% volume ratio and the isodecyl alcohol of 8% volume ratio, 50 DEG C, to compare O/A be under 1 condition, use again the back extraction of 150g/L sulfuric acid to solution, obtain through electrodeposition the cathode zinc that purity is higher.
6. comprehensive utilization according to claim 1 is from the method for the iron vitriol slag of wet zinc-making system, and in its step (5), optimized leaching condition is: the concentration of sodium hydroxide solution is 30%, and temperature is 150 DEG C, extraction time 1 hour.
CN201010503846.9A 2010-10-12 2010-10-12 Clean metallurgic comprehensive utilization method of iron vitriol slags CN102443701B (en)

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CN102718267B (en) * 2012-07-18 2013-11-20 广西大学 Method for preparing black iron oxide by utilizing yellow ammonium iron alum slag
CN103114205B (en) * 2012-12-07 2014-06-25 金川集团股份有限公司 Two-step method for extracting valuable metal nickel and copper from sodium jarosite slag
CN103589861B (en) * 2013-11-27 2015-07-22 昆明理工大学 Method for microwave sulfating roasting-water leaching treatment of jarosite slag
CN104087754B (en) * 2014-07-07 2016-06-22 中南大学 A kind of zinc ferrite calcination for activation-thing regulates and controls the method that zinc-iron separates mutually
CN104946903A (en) * 2015-07-06 2015-09-30 中南大学 Method for recovering metal resource from zinc calcine through reduction roasting-leaching-zinc sinking
CN105366728B (en) * 2015-11-03 2017-09-29 中南大学 A kind of method that iron vitriol slag prepares iron oxide red
CN105886762A (en) * 2016-04-15 2016-08-24 包头稀土研究院 Cyclic utilization method of NH4Cl solution in precipitating and separating Sm<3+> and Zn<2+> by using ammonium bicarbonate
CN106521169B (en) * 2016-11-05 2018-03-13 北京工业大学 A kind of method of argentiferous lead slag for comprehensive recovery
CN107324358B (en) * 2017-06-20 2019-03-12 谭宏斌 A kind of iron vitriol slag low-temperature decomposition and the method that resource is separately recovered
CN107354302B (en) * 2017-07-16 2019-11-05 六盘水中联工贸实业有限公司 A kind of comprehensive recovering process of the ash of zinc die casting alloys containing aluminium
CN107746058A (en) * 2017-10-19 2018-03-02 玉溪师范学院 A kind of method for efficiently producing silica dioxide gel using copper smelting slag
CN109250760B (en) * 2018-07-25 2020-10-09 桂林理工大学 Method for preparing high-performance sheet-shaped porous structure zinc ferrite negative electrode material by using vitriol slag sulfuric acid leaching solution and application
CN110016547B (en) * 2019-04-23 2020-11-13 王柯娜 Comprehensive utilization method of jarosite slag
CN109957656A (en) * 2019-05-21 2019-07-02 安徽铜冠有色金属(池州)有限责任公司 A kind of zinc hydrometallurgy iron vitriol slag recycling and the technique for recycling dilute scattered noble metal

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